Hair bleaching composition containing water-soluble amino and quaternary ammonium polymers

ABSTRACT

A hair treating composition containing, in addition to a bleach, a water soluble secondary or tertiary amine polymer or a polymer of diallylamine or a quaternary polymer of diallyldialkylammonium salts improves the surface characteristics of hair.

This is a division of application Ser. No. 577,616 filed May 14, 1975,now U.S. Pat. No. 3,986,825, which itself was a division of applicationSer. No. 267,664, filed June 29, 1972, now U.S. Pat. No. 3,912,808.

The latter application is a continuation-in-part of application Ser. No.14,205 filed Feb. 25, 1970, now abandoned.

This invention relates to hair treating compositions for bleaching,waving or straightening, or coloring or dyeing hair and morespecifically to such compositions containing high molecular weight watersoluble polymers having a multiplicity of amino or of quaternary saltgroups.

Modern day living results in exposure of individuals to increasingamounts of sunlight, chlorine water, harsh detergents and chemicalspecialty products. Because of this, hair treating products must becapable of leaving the hair with luster and softness while overcomingnatural or induced harshness and dryness. This is in addition to aproduct's primary purpose whether it be to impart or maintain a hairstyle or to alter the natural color of the hair. There is, in each case,the corollary requirement that the hair be left with an improvedappearance and feel. In those types of products where the hair issubjected to chemical reaction, it is important that the cosmetic becapable of restoring the hair as nearly as possible to its originalstate in relation to the feel of the hair, and frequently by its ease ofcombing.

There have been in the past several means of achieving this end. One ofthe simplest means of doing so has been to dissolve a conditioningmaterial in a suitable solvent or vehicle. In some cosmetic forms, afterapplication, the evaporation of solvent deposits the conditioningmaterial. This method has been useful in the deposition of natural gums,certain of the synthetic polymers, and a few protein derivatives. Ashortcoming of such systems, when aqueous, is that any such materialthat can be dissolved in water is equally subject to subsequent removalby simple washing. Water insoluble materials deposited on hair fromorganic solvent, while more resistant to water removal, require that thehair be subjected to the reaction of organic solvent materials capablethemselves of extracting natural constituents of hair. Non-aqueousoleaginous mixtures have sometimes been used to deposit coatings ofconditioning materials on hair. The standard hot oil treatment for hairand some hair grooms are representative. Such oil coatings, however,whether of mineral, animal or vegetable origin, are generally too greasyto satisfy modern tastes. Application of conditioning materials to hairfrom emulsion systems is often practiced enabling many materials to beused which would otherwise be difficult to apply. As in the previouslyindicated case of application from aqueous solvent systems, thedeposited film is generally easily removable by simple water washing,the original emulsifying materials present in the composition alsoremaining behind to reduce the binding potential of the conditioningmaterial to hair.

One of the more interesting and most widely used means for overcoming aharsh feeling in human hair is by the deposition of cationic materialswhich are absorbed by the protein structure of the substrate. Especiallyuseful have been the cationic fatty quaternary compounds having fattychain lengths of approximately 8 to 18 carbon atoms. These materialswhich form the basis of many of the conditioning hair rinse productsfound on the market, though substantive to skin and hair, cannotwithstand, to any substantial extent, the action of most detergentmaterials used for personal cleansing. While these materials are animprovement over the older modes of conditioning described above, theycan soften the hair excessively leaving it unmanageable and with a lackof body. It has not generally been found helpful to simply reduce theconcentration of the quaternary material since to do so would reduce thecombing benefits and/or conditioning properties imparted by suchproducts to the hair. Furthermore, because many of the most widely usedproducts for treating hair contain anionic surfactants and becausecationic materials are usually inactivated by reaction with anionicsurfactants, it is customary to employ cationic materials only as aseparate composition such as a post shampoo rinse separately applied.There has been disclosed another means of depositing conditioningmaterials on hair. U.S. Pat. No. 3,313,734 and Canadian Pat. No. 762,893describe cosmetic compositions containing certain polymers havingcationic sites. The compositions yield a fine precipitate of the polymercomponents upon dilution with water. This precipitate adheres to thesurface of the hair shaft, thereby altering surface properties of thehair fibers. This effect, as described in the above patents, is limitedhowever to shampoo compositions and produces in many instances anundesirably heavy deposit of material which leaves the hair feelingcoated and unclean.

It has now been discovered that the surface characteristics of hair canbe modified and its condition improved by applying thereto a compositioncontaining certain water soluble polymers containing secondary andtertiary amino or quaternary ammonium groups. These polymers areincorporated in the hair treating composition itself instead of beingused in the form of separate solutions separately applied. The hairtreating composition in each case includes in addition to water and thewater-soluble polymer (as defined below) a coloring agent i.e. a hairdye or hair dye precursor; or a hair waving or straightening agent suchas a reducing agent capable of breaking the disulfide linkages in hairkeratin; or a peroxide such as hydrogen peroxide in the case of hairbleaching compositions or neutralizing compositions (for use inconjunction with waving or straightening compositions). Also present inthe case of the hair coloring and hair bleaching compositions are asurface active agent such as a soap or detergent and sufficient watermiscible aliphatic hydroxylated solvent (or a mixture of such solventwith a water-soluble salt inert to the ingredients and to hair) tomaintain the composition homogeneous i.e. in a single phase.

The polymers are equally effective when an anionic surface active agentsuch as soap, etc. is present as when only cationic, nonionic, orampholytic agents are present despite the fact that ionic interactionwould be expected to lead to the formation of an inactive and insolublecatan wax. The polymer can be used effectively in amounts rangingupwardly from 0.05% by weight of the total composition. There is nocritical upper limit to the amount of polymer which may be present, andamounts as great as 40% by weight of the composition or even more may beused, particularly when application of the composition to the hair isfollowed by a water rinse. If the composition is supplied in suchconcentrated form, however, it is generally desirable to dilute it withwater to a polymer content of 0.5 to 15% by weight before use. Thecompositions in which the polymers may be effectively employed may varywidely in acid or base content, having a pH, when in water, from 1.5 to11.5. The polymers are effective to alter the surface characteristics ofthe hair and maintain the desired conditioned effect even though theapplication of the composition is followed, intentionally orunintentionally, by a water rinse. Indeed, the conditioning effectproduced by incorporating these polymers in a hair treating compositionis remarkably durable, persisting in many cases through severalsuccessive rinses and even through successive washings with aconventional detergent or shampoo composition. This is true even in thecase of hair coloring and hair bleaching compositions which contain soapor detergent which in itself would be expected to remove the polymereven if no shampoo were subsequently used.

In the hair coloring compositions of the present invention the coloringagents may be any of the known acidic, basic, or disperse dyes oroxidation dye intermediates; they may be present in any effective amountranging from 0.03 to 10% by weight of the total composition, dependingon the type of dye and the desired color result, as is well known tothose skilled in the art. When the coloring agent is an oxidative dyeintermediate it is usually desirable to mix with the composition beforeapplying it to the hair an oxidizing agent such as hydrogen peroxide,sodium peroxide, urea hydrogen peroxide or the like, in accordance withconventional practice, in an amount effective to develop the desiredcolor.

The hair bleaching compositions contain in aqueous solution an oxidizingagent such as hydrogen peroxide or urea hydrogen peroxide together withconventional stabilizers such as phenacetin and/or sodium stannatetogether, if desired, with a suitable conventional buffer to maintainthe pH at the desired level of 2.5 to 6.5. The amount of oxidizingagent, in accordance with conventional practice, may be from 0.5 to 20%by weight of the total composition.

The hair waving and straightening compositions of the present inventioncontain aqueous solutions of reducing agents capable of reducing thedisulfide linkages in hair keratin, of which many are well known such aswater soluble mercaptans e.g. sodium or ammonium thioglycolate,magnesium thioglycolate, thioglycerol, sodium or potassium borohydride,sodium or ammonium sulfite, etc. The amount of such reducing agent, asis well known, may be from 0.5 to 10% by weight of the totalcomposition. A variety of conventional additives for such compositionsmay also be present.

The neutralizer compositions of the present invention, which are usedfor applying to the waved or straightened hair to restore the disulfidelinkages in the hair keratin, contain in aqueous solution any of theoxidizing agents conventionally employed for this purpose, such ashydrogen peroxide, urea hydrogen peroxide, sodium carbonate peroxide,sodium or potassium bromate, sodium perborate, or sodium hypochlorite;the neutralizer compositions used with sulfite waving or straighteningcomposition may contain simply sodium sesquicarbonate instead of anoxidizing agent.

The surface active agent present as an essential ingredient of the haircoloring or hair bleaching composition may be a soap, i.e. an alkalimetal, ammonium or amine salt of a long chain aliphatic acid,particularly a fatty acid, such as the sodium, potassium, lithium orammonium salts or the salts of such amines as mono-, di-, ortri-ethanolamine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol,diethylamine, mono- and diisopropanolamine, polyglycolamine,N-ethylmorpholine with such acids as capric, undecylic, lauric,myristic, palmitic, stearic, oleic, linoleic, ricinoleic, dimer ortrimer acids produced by polymerization of C₁₈ fatty acids,hydrogenerated rosin acids, lanolin acids, phenylstearic acid, coconutfatty acids, tallow fatty acids, or castor fatty acids includinghydroxyricinoleic acid and the like. The surface active agent may alsobe an anionic material such as sodium di-(2-ethylhexyl) phosphatedioctyl sodium sulfosuccinate, sodium dodecylbenzenesulfonate, sodiumlauryl sulfate, or disodium ethoxylated alcohol half ester ofsulfosuccinic acid. Cationic surface active agents can also be used,such as stearyldimethylbenzylammonium chloride, stearic aminoamide,dimethyldialkylammonium chlorides in which each alkyl group has from 8to 18 carbon atoms, polyethoxylated quaternary ammonium salts,amidoamine oxide derivative of lauric acid, or cetylpyridinium chloride.Among nonionic surface active agents which can be used are variouscondensates of alkylene oxides, e.g. ethylene oxide or propylene oxidewith other molecules, each condensate molecule containing from 5 to 500alkylene oxide units, such as octylphenoxypolyethoxyethanol, condensatesof ethylene oxide with hydrophobic bases formed by condensing propyleneoxide with propylene glycol, mono- and diglycerides of long chain fattyacids, sorbitan esters of long chain fatty acids, polyoxyethylenesorbitan monolaurate, monopalmitate or monostearate, polyoxyethylenelauryl ether, polyoxyethylene stearyl ether, lauric diethanolamide,dimethyloctadecylamine oxide, nonylphenylpolyethylene glycol ether,ethylene oxide condensates with long chain fatty amides, acetylatedlanolin alcohols, or coconut fatty acid alkanolamides. Amphotericsurface active agents useful in the compositions of the presentinvention include imidazoline derivatives made by condensing polyamideswith long chain fatty acids including lauric, capric, oleic and stearicsold under the trade name Miranol in the form of various salts such asthe potassium, sodium, mono-, di-, or triethanolamine orisopropanolamine salts, N-coco-beta-aminopropionic acid or its sodiumsalt, disodium N-lauryl-beta-iminodipropionate;N-lauryl/myristyl-beta-aminopropionic acid, or a complex polyalkylamidoimidazolinium sulfate sold under the trade name Soromine CAZ-75. Any ofthese surface active agents may be present as an optional ingredient inthe hair waving or straightening compositions or neutralizingcompositions of the present invention. The surface active agents can beused in amounts from 0.1 to 0.5% by weight of the total composition,preferably from 0.3 to 25% by weight.

When a surface active agent is present in any of the compositions, theremust also be present sufficient water miscible hydroxylated organicprimarily aliphatic solvent, or a mixture of such solvent with inertwater-soluble salt, to solubilize all of the ingredients. Among suitablesolvents are ethanol, isopropanol, benzyl alcohol, hexylene glycol,hexanol, 2-methylpentanol, 2-ethylbutanol, diethylene glycol,tetraethylene glycol, propylene glycol, 1,5-pentanediol, polyethyleneglycol, glycol ethers such as 2-ethoxyethanol, 2-phenoxyethanol,monoethylether of diethylene glycol, monobutyl ether of diethyleneglycol, monobutyl ether of diethylene glycol, monobutyl ether of1,2-propanediol, monomethyl ether of dipropylene glycol, or1-butoxyethoxy-2-propanol. The minimum amount of such solvent needed toensure homogeneity will vary depending upon the identity and quantity ofother ingredients present but in general may range from 1 to 90% byweight of the total composition.

The water soluble salts which can be used in conjunction with thehydroxyl-containing solvent to increase its effectiveness include thosewhich are chemically inert to the remaining ingredients of thecomposition as well as to the hair such as the sodium, potassium,lithium, ammonium or lower alkanolamine chlorides, bromides, sulfates,or acetates. They can be used in amounts from 0.01 to 15% by weight ofthe total composition, preferably from 0.05 to 5% by weight.

The polymers useful in the present invention are high molecular weightwater-soluble amino and quaternary ammonium homopolymers and copolymershaving as constituents of the chain or backbone of the polymer molecule(apart from end groups which terminate each such chain and which have noimportant effect upon the properties and characteristics of the polymer)units of the following formulas: ##STR1## where R is hydrogen or methyl;R' is hydrogen, or an alkyl group having one to twenty-two carbon atoms,or a lower hydroxyalkyl group having from one to five carbon atoms, or alower alkyl group containing a terminal amido group such asbeta-propionamido; and wherein A and B are independently (i.e. eitherboth the same or different) alkyl groups having one to twenty-two carbonatoms, lower hydroxyalkyl groups having from one to five carbon atoms,and lower alkyl groups containing terminal amido groups such asbeta-propionamido; and wherein A and B together with N are piperidinylor morpholinyl groups. Salts of Polymer I such as the hydrochloride,hydrobromide or sulfate are the full equivalent of Polymer I. In thecase of both the polymer of Formula I and the polymer of Formula II thepreferred homopolymers and copolymers are those in which R is hydrogen;and in the case of the polymer of Formula II the preferred homopolymersand copolymers are those in which A and B are independently lower alkylgroups having from 1 to 5 carbon atoms or in which A and B form togetherwith nitrogen atom a piperidinium or a morpholinium group. These linearhomopolymers and copolymers have a molecular weight from about 20,000 to3,000,000. In the case of homopolymers, all of the units in the polymerchain are identical, while in the case of copolymers, the units, whilehaving the structure defined above, are not all identical to each otherand in addition, may contain the structures of acrylamide or diacetoneacrylamide as described below. Any of a wide variety of nontoxic orcosmetically acceptable anions, organic as well as inorganic, may bepresent in the polymer and associated with the quaternary ammoniumcationic groups, among which are, for example, acetate, borate, bromide,chloride, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate,and succinate. The homopolymers and copolymers of Formula I can beprepared as described in Butler et al U.S. Pat. No. 2,926,161 bypolymerizing the appropriate diallylamine or amine salt. Thehomopolymers and copolymers of Formula II can be made by polymerizingdiallyldialkylammonium chloride or bromide or other appropriate diallylmonomeric ammonium salts using a free radical generating polymerizationcatalyst such as a peroxide, then using an anion exchange columntechnique for exchanging the anion, if desired, and are described inU.S. Pat. Nos. 3,288,770 and 3,412,019. If a polymer of a chloride isdissolved in an aqueous solution or in a cosmetic base containing saltsof any other anions, of course, the resulting solution contains bothanions, each being associated to some extent with the quaternaryammonium groups of the polymer. Other monomers which can becopolymerized with diallylamine or with the desired diallylammonium saltto form copolymers containing units of Formula I or II includeacrylamide and diacetone acrylamide. The polymer units derived fromacrylamide have the structure ##STR2## while those derived fromdiacetone acrylamide have the structure ##STR3## The amount of theseacrylamide-type monomers incorporated in the copolymer may vary from 5%to 95% by weight of the total monomers; The copolymers can be made bysubjecting the mixture of monomers to the same polymerization conditionsas used in making the homopolymers. It generally makes no difference, sofar as the present invention is concerned, whether the polymer orcopolymer containing a particular desired anion or combination of anionsis prepared in pure form before being mixed with the hair treatingcomposition or whether the desired anions are introduced into thecomposition in the form of other salts. It is usually most convenient toemploy the least expensive salt of the polymer which is readilyavailable, regardless of the anion which it contains, and add thedesired anions in the form of other less expensive salts. Hair treatingcompositions, as is well known, contain any of a wide variety ofnon-toxic anions, numerous examples of which are given herein.Particularly preferred is a polymer of a diallyldimethylammonium salt,that is, a polymer having repeating units of the formula given abovewhere A and B are both methyl groups, all of the units being identical.

The following specific examples are intended to illustrate more fullythe nature of the present invention without acting as a limitation uponits scope.

EXAMPLE 1

A conventional hair straightening lotion base was prepared having thefollowing composition:

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Ammonium bisulfite      10.0                                                  Urea                    15.0                                                  Isopropanol             4.0                                                   Hydroxyethylcellulose   1.0                                                   Ammonium hydroxide to pH                                                                              7.1                                                   Water to                100.0                                                 ______________________________________                                    

To one portion of the lotion was added 0.5% by weight of a polymer ofdiallyldimethylammonium chloride in the form of a 40% by weight aqueoussolution having a viscosity of about 12,500 centipoises. Samples of thelotion with and without the added polymer were then employed to treatseparate heads of hair under identical conditions, viz. application toclean hair and allowing to stand 20 minutes covered with a turban,application of additional lotion and allowing to stand for another 20minute period covered with a turban, rinsing with water, applying aneutralizer a 4.5% aqueous solution of sodium sesquicarbonate dihydrate,and finally rinsing with water. It was found that the hair treated withthe polymer-containing lotion was soft, lustrous and easy to comb bothwet and dry as contrasted to the harsh feeling, difficult-to-comb hairresulting from the other lotion. The difference was still apparent afterfour weeks and several intervening shampoos. When as little as 0.05% ofthe polymer or as much as 2.0% were used, the results were very similar.

It has been found that the presence of relatively large quantities ofinorganic salts commonly employed in cosmetic bases, such as sodiumcarbonate, sodium sulfate, sodium phosphate, or sodium tripolyphosphatehas little or no effect upon the conditioning properties of a 10% byweight aqueous solution of a polymer of diallyl dimethyl ammoniumchloride which has, in the form of a 40% by weight aqueous solution, aviscosity of 5000cps. Similar results were observed in the case of a 10%solution of a higher molecular weight polymer of the same species whichexhibited a viscosity of 130,000 cps. in 40% aqueous solution.

EXAMPLE 2

Results similar to those obtained in Example 1 were obtained bydissolving 2% by weight of the same polymer in the neutralizer solutioninstead of mixing polymer with the straightening lotion.

EXAMPLE 3

A hair waving lotion base was prepared having the following composition:

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Ammonium thioglycolate  7.8                                                   Diisopropanolamine      6.7                                                   Polyoxyethylene(25)oxypropylene(5)                                            monostearate            0.5                                                   Perfume                 0.125                                                 Water to                100.0                                                 ______________________________________                                    

To one portion of the lotion was added 0.5% by weight of the polymerused in Example 1. Samples of the lotion with and without the addedpolymer were then employed to treat separate heads of hair underidentical conditions, viz. application of the lotion to hair previouslyshampooed, winding of the hair on curlers, application of additionallotion to the hair and allowing to stand for 15 minutes, rinsing withwater and allowing to stand covered with a turban for 30 minutes. Aneutralizer consisting of an aqueous solution containing 1.2% hydrogenperoxide and 0.05% of stearyl dimethyl benzyl ammonium chloride was thenapplied to the hair on the curlers, the hair was removed from thecurlers and the neutralizer again applied. The hair waved with thelotion containing the polymer was soft, lustrous, and easy to comb bothwet and dry in contrast to the hair waved with the other lotion whichwas harsh, difficult to comb, and readily tangled. The marked differencein conditioning or surface characteristics of the hair persisted evenafter both heads had been subjected to six successive shampoos.

Similar results were obtained by dissolving the polymer in theneutralizer instead of in the lotion, as in Example 2.

EXAMPLE 4

A hair bleaching base composition containing the polymer of Example 1was prepared by mixing 1 volume of composition A and 2 volumes ofsolution B with 10 volumes of 6% aqueous hydrogen peroxide solution, asfollows:

    ______________________________________                                        Composition A                                                                 Ingredient              Weight Percent                                        ______________________________________                                        Ammonium Persulfate     80.0                                                  Sodium Silicate         15.0                                                  Sodium Lauryl Sulfate   5.0                                                                           100.0                                                 Solution B                                                                    Ingredient              Weight Percent                                        ______________________________________                                        Oleic acid              35.0                                                  Ammonium hydroxide (29%)                                                                              11.0                                                  Isopropanol             15.0                                                  Polymer of Example 1    4.0                                                   Octylphenoxypolyethoxy(9-10)                                                                          15.0                                                  ethanol                                                                       Water                   20.0                                                                          100.0                                                 ______________________________________                                    

The composition was applied to hair and allowed to stand for periods oftime from 30 to 90 minutes depending upon the extent of bleachingdesired. After rinsing and shampooing the hair displayed the samesuperior condition as was observed in the hair of the precedingexamples, in contrast to the undesirable condition of hair bleached witha similar composition omitting the polymer.

EXAMPLE 5

A hair dyeing base composition containing the polymer of Example 1 wasprepared by mixing 6% aqueous hydrogen peroxide with an equal volume ofthe following solution:

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Oleic acid              20.0                                                  Ammonium hydroxide (29%)                                                                              7.6                                                   Octylphenoxypolyethoxy(9-10) ethanol                                                                  20.0                                                  Isopropanol             18.0                                                  Polymer of Example 1    5.0                                                   Ethylenediaminetetraacetic acid                                                                       0.05                                                  Sodium Sulfite          0.05                                                  p-Phenylenediamine      0.1                                                   Resorcinol              0.02                                                  Water to                100.0                                                 ______________________________________                                    

The composition was applied to the hair, allowed to stand about 20minutes, rinsed with water and shampooed. The condition of the hair wasmarkedly superior to that of hair treated with the same compositionomitting the polymer, the differences being similar to those of thepreceding examples.

EXAMPLE 6

An oxidative hair dyeing base composition containing our polymer wasprepared by mixing 6% aqueous hydrogen peroxide with an equal volume ofthe following solution:

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Oleic acid              20.0                                                  Ammonium hydroxide (29%)                                                                              7.6                                                   Octylphenoxypolyethoxy(9-10) ethanol                                                                  20.0                                                  Isopropanol             18.0                                                  Polymer of Example 1    5.0                                                   Ethylenediaminetetraacetic acid                                                                       0.05                                                  Sodium sulfite          0.05                                                  p-Phenylenediamine      0.1                                                   Resorcinol              0.02                                                  Water to                100.0                                                 ______________________________________                                    

The composition was applied to the hair, allowed to stand about 20minutes at room temperature, rinsed with water and shampooed. The hairwas dyed a light ash blonde color. In order to ascertain the presence ofthe conditioning effect, the following test is performed. Tresses areprepared using hair that has been bleached and waved. This type of hairis difficult to comb either wet or dry and represents a realisticstandard for the evaluation of conditioning treatments. An untreatedtress is marked as a control and is evaluated both for wet and drycombing properties. A number of tresses from the same hair lot (toeliminate variations from lot to lot) are then subjected to the hairtreating composition to be tested. The evaluations are made by a panelof cosmetic scientists or beauty operators. The tresses are combed andranked on a 1 to 5 scale, where 1 is the poorest and 5 is the best. Thechange in rating from the control value is an indication of theeffectiveness of the conditioning treatment. Persistence of high ratingsafter a series of shampoos indicates the continued existence ofconditioning on the tress. The ratings reported in the followingexamples are based on the above scale and are for wet combings unlessspecified otherwise. The condition of the hair treated with thecomposition of this Example 6 was markedly superior (rating 4) comparedto that of hair treated with the same composition omitting the polymer(rating 2).

EXAMPLE 7

An aerosol oxidative hair dyeing composition was prepared to be used ina two compartment aerosol container described in U.S. Pat. No.3,241,722:

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Oleic acid              8.7                                                   Monoethanolamine        5.0                                                   Octylphenoxypolyethoxy(9-10)ethanol                                                                   6.0                                                   Isopropanol             25.0                                                  Ethylenediaminetetraacetic acid                                                                       0.05                                                  Sodium Sulfite          0.05                                                  Polymer of Example 1    1.0                                                   Sodium Chloride         1.0                                                   p-Phenylenediamine      0.1                                                   Resorcinol              0.05                                                  Water to                100.0                                                 ______________________________________                                    

To 93 grams of the above composition was added 9.3 grams of 50/50 blendof propellants dichlorodifluoromethane and dichlorotetrafluoroethane.About 27 grams of a 16% aqueous hydrogen peroxide solution was placed inthe inner compartment while the other composition together with thepropellant mixture was placed in the outer compartment. Tresses dyed for20 minutes at room temperature with this composition were a medium ashblonde. The condition of the tresses was excellent and persisted throughat least four shampoos.

EXAMPLE 8

An aerosol oxidative hair dyeing composition was prepared and employedin the two compartment container described in U.S. Pat. No. 3,241,722.To 93 grams of the composition described below was added 9.3 grams of a50/50 blend of propellants as described in Example 7 and placed in theouter portion of the container.

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Oleic acid              8.7                                                   Monoethanolamine        6.7                                                   Isopropanol             20.4                                                  Octylphenoxypolyethoxy(9-10)ethanol                                                                   0.4                                                   Polymer of Example 1    0.5                                                   p-Phenylenediamine      0.5                                                   Resorcinol              0.3                                                   2,4-diaminoanisole      0.05                                                  p-aminophenol           0.3                                                   Water - q.s.            100.0                                                 ______________________________________                                    

27 grams of 6.15% aqueous hydrogen peroxide was placed in the innercontainer. The above creamy composition was applied to blonde hairtresses, allowed to remain for 20 minutes at room temperature andrinsed. The tresses were dyed a dark ash brown. Conditioning wasevaluated after shampooing and rated as 4.0.

EXAMPLE 9

An oxidative hair toning composition was prepared according to thefollowing recipe and mixed with an equal weight of 6% aqueous hydrogenperoxide.

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Triethanolamine         7.0                                                   Isopropanol             16.0                                                  Polymer of Example 1    2.0                                                   Polyoxyethylene(2)oleyl ether                                                                         18.0                                                  Polyoxyethylene(10)oleyl ether                                                                        2.0                                                   Ethylenoxide(12) condensate of a C-18                                         fatty amine             10.0                                                  Sodium Oleate           5.0                                                   p-Phenylenediamine      0.25                                                  Resorcinol              0.05                                                  Water to                100.0                                                 ______________________________________                                    

After 20 minutes contact at room temperature with blonde hair followedby rinsing and shampooing, the tress was toned a medium ash blonde. Acombing evaluation rated the hair 3.5. A control without the polymer wasrated 2.2. After two weeks, the original tress was again shampooed andevaluated and was rated at 3.2.

EXAMPLE 10

An aerosol oxidative hair dyeing composition was prepared and employedin the two compartment container described in U.S. Pat. No. 3,241,722.To 93 grams of the composition described below was added 9.5 grams of a50/50 mixture of propellants as described in Example 7; the mix wasplaced in the outer portion of the container. 27 grams of aqueoushydrogen peroxide (6%) was placed in the inner container.

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Oleic Acid              17.4                                                  Octylphenoxypolyethoxy(9-10)ethanol                                                                   2.0                                                   Isopropanol             15.0                                                  Monoethanolamine        6.9                                                   Polymer of Example 1    0.6                                                   p-Phenylenediamine      0.06                                                  Resorcinol              0.06                                                  Water q.s. to           100.0                                                 ______________________________________                                    

Blonde hair tresses were treated with the creamy composition dischargedfrom the container, being left in contact with it at room temperaturefor 25 minutes, rinsed and shampooed. The hair was dyed to a light ashblonde. The tresses were combed and rated 4.5. A similar compositionwithout the polymer produced a rating of 2.0 on similarly treatedtresses.

EXAMPLE 11

A permanent hair color was prepared using oxidation dye intermediateswithout hydrogen peroxide:

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Polydiallyldiethylammonium Chloride                                                                   3.0                                                   Hexylene Glycol         10.0                                                  Sodium Chloride         1.0                                                   Sodium Coco-H-methyltauride                                                                           5.0                                                   p-Phenylenediamine      3.0                                                   p-Aminophenol           1.0                                                   Resorcinol              0.5                                                   Water q.s. to           100.0                                                 ______________________________________                                    

The two phase product was shaken before use and applied to blondetresses for 15 minutes. The hair was rinsed and found to be dyed anashen light brown. After two shampoos the combing rating was still 4.5.

EXAMPLE 12

A disperse dye composition for dyeing human hair was prepared andevaluated on blonde bleached/waved tresses.

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Polyoxyethylene(23)lauryl ether                                                                       5.00                                                  Lauric diethanolamide   5.00                                                  C. I. Disperse Black, C. I. No. 11365                                                                 1.00                                                  Polydiallyldimethylammonium                                                   chloride (viscosity 500 cps.)                                                                         20.00                                                 Isopropanol             25.00                                                 Perfume                 0.10                                                  Water q.s. to           100.0                                                 ______________________________________                                    

After 30 minutes contact with the composition, the hair was dyed agolden blonde. After two shampoos, the combing rating of the hair wasstill 4.0.

EXAMPLE 13

The following disperse dye composition for dyeing human hair wasprepared and evaluated on blonde bleached/waved tresses.

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Polydiallyldimethylammonium                                                   chloride (viscosity 128000 cps.)                                                                      20.00                                                 Sodium Chloride         1.00                                                  Benzyl Alcohol          4.00                                                  C. I. Disperse Black 1, C. I. No. 11365                                                               1.00                                                  Sodium lauroylsarcosinate                                                                             13.17                                                 Perfume                 0.1                                                   Water q.s. to           100.00                                                ______________________________________                                    

The composition was applied and worked up to a lather on tresses andallowed to stand for 30 minutes. Water was applied and worked up to alather again and rinsed. The hair was dyed a golden blonde and after twoshampoos, had a wet rating of 4.0.

EXAMPLE 14

A basic dye hair toning composition was prepared and evaluated onbleached-waved hair.

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Stearyldimethylbenzylammonium                                                 chloride                1.8                                                   Polymer of Example 1    4.5                                                   Methylene Blue          0.045                                                 Hexylene Glycol         25.00                                                 Polyethyleneoxide, M.W. 100,000                                                                       0.45                                                  Perfume                 0.1                                                   Water q.s. to           100.0                                                 ______________________________________                                    

Bleached-waved hair was treated for 30 minutes, water-rinsed, andshampooed. The hair was toned a pleasant pale green, actually blue on ayellow substrate, and after two shampoos was rated 3.25.

EXAMPLE 15

A hair lightener composition was prepared having the followingcomposition. Lighteners usually produce roughened hair and conditioningin these systems is particularly advantageous.

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Oleic Acid              20.00                                                 2-Amino-2-methyl-1-propanol                                                                           9.31                                                  Polymer of Example 1    5.00                                                  Ethanol                 10.00                                                 Perfume                 0.20                                                  Water q.s. to           100.0                                                 ______________________________________                                    

To one part by weight of the above composition was added two parts ofaqueous 6% hydrogen peroxide and the mixture was applied to brown hairfor 30 minutes. The hair was water-rinsed and found to be lightenedabout one shade and was readily combed. Using the same composition onbleached-waved hair, the conditioning was found to be 4.5 to 5.0 aftertwo shampoos.

EXAMPLE 16

The same composition was prepared as in Example 15 except that insteadof mixing in two parts of the hydrogen peroxide solution there was mixedin 0.5% by weight of C.I. Basic Brown 2 (C.I. No. 21030). Thecomposition was applied to white hair for 30 minutes, rinsed andshampooed. The hair was colored a light auburn. Bleached-waved hair towhich the same composition was applied had a combing rating of 5.0 aftertwo shampoos.

EXAMPLE 17

The following conditioning acid dye composition was prepared andevaluated on white hair.

    ______________________________________                                        Ingredient           Weight Percent                                           ______________________________________                                        Miranol C2M Conc*    8.00                                                     Polymer of Example 1 5.00                                                     F. D. & C Blue No. 2, C.I. No. 73015                                                               0.50                                                     Benzyl alcohol       4.50                                                     Perfume              0.10                                                     Water q.s. to        100.0                                                    ______________________________________                                    

The composition was applied to white hair for 30 minutes after which alather was worked up. After rinsing, the hair was found to be toned apale blue. The color was only semi-permanent and much was removed aftertwo shampoos. Evaluation of the composition on bleached-waved hair aftertwo shampooings showed a rating of 4.5 to 5.0.

EXAMPLE 18

The following aerosol basic-dye hair conditioning composition wasprepared and evaluated on white hair for color and condition.

    ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Polydipropyldiallylammonium                                                   chloride                4.0                                                   Ethanol                 85.9                                                  Condensate of 10% ethylene oxide                                              and 90% propylene oxide with                                                  propylene glycol (M.W. about                                                  1100)                   10.0                                                  Methylene Blue          0.10                                                  ______________________________________                                    

Ninety parts by weight of the above composition are packaged with 10parts of propellant mixture consisting of trichloromonofluoromethane45%, dichlorodifluoromethane 45% and isobutane 10%, in an aerosolcontainer. The container was shaken prior to use and the composition wasapplied to damp hair and left for 30 minutes then water-rinsed andshampooed. The hair was dyed a light blue. After two shampoos, thecondition of the hair was still rated 3.0.

EXAMPLES 19--21

The following compositions (Table I) were prepared with four differentpolymers, the compositions being suitable for use as hair dyes by theaddition of the conventional desired dye. The compositions, eachcontaining a different polymer, were then mixed with an aqueous 16%hydrogen peroxide solution in the proportion of 3.5 parts by weight ofthe composition to 1.0 part of peroxide solution, and the mixture leftin contact with hair tresses, one virgin hair which had never beenbleached or chemically waved, the other bleached and waved hair, for 20minutes at room temperature, then rinsed.

Each hair tress was then rated for condition with the results set forthin Table II. In this case the hair tresses were rated both while wet(WC) and after drying (DC) as well as being rated again after oneshampoo and rinse (1S) and after three (3S).

                  Table I                                                         ______________________________________                                        Ingredient            Percent by Weight                                       ______________________________________                                        Oleic acid            8.7                                                     Monoethanolamine      5.0                                                     Triton X-100 (Octylphenoxypolyethoxy                                          (9-10)ethanol)        1.0                                                     Triton X-35 (Octylphenoxypolyethoxy                                           (3-4)ethanol)         5.0                                                     Isopropanol           25.0                                                    EDTA                  0.05                                                    Sodium sulfite        0.05                                                    Polymer               1.0                                                     Water                 q.s.                                                    ______________________________________                                    

                                      TABLE II                                    __________________________________________________________________________                 Hair Condition                                                                Virgin                Bleached/Waved                             __________________________________________________________________________    Polymer      WC  DC  WC(1S)                                                                             WC(3S)                                                                             WC  DC  WC(1S)                                                                             WC(3S)                            __________________________________________________________________________    Polymer of Example 1                                                                       4.5 3.5 4.5  4.0  4.3 4.0 4.0  3.0                               Polydipropyldiallyl-                                                          ammonium chloride                                                                          4.0 3.0 3.5  3.5  2.8 4.0 2.5  2.5                               Polydiallylpiperidinium                                                       chloride     4.5 3.0 4.5  3.5  4.3 4.0 3.5  2.5                               Polydiallylamine                                                              hydrochloride                                                                              4.5 3.0 4.5  4.0  4.3 3.5 4.0  3.0                               None         3.5 3.0 3.5  3.5  2.5 4.0 2.5  2.5                               __________________________________________________________________________

EXAMPLES 22-32

Hair bleaching compositions were prepared by mixing with one part byweight of a 16% aqueous hydrogen peroxide solution 3.5 parts of each ofseveral compositions having the following recipe, the polymer in eachcase being different as listed in Table III.

                  Recipe                                                          ______________________________________                                        Ingredient              Weight Percent                                        ______________________________________                                        Oleic acid              9.0                                                   Monoethanolamine        5.1                                                   Octylphenoxypolyethoxy (9-10) ethanol                                                                 1.0                                                   Octylphenoxypolyethoxy (3-4) ethanol                                                                  5.0                                                   Isopropanol             15-37                                                 Cationic polymer        1.0                                                   Water q.s. to           100.0                                                 ______________________________________                                    

                  TABLE III                                                       ______________________________________                                        Polydimethyldiallylammonium chloride                                          Polydiallylamine hydrochloride                                                Polydipropyldiallylammonium chloride                                          Polydiallylpiperidinium chloride                                              Copolymer (50:50) of dimethyldiallylammonium chloride                         and acrylamide                                                                Copolymer (75:25) of dimethyldiallylammonium chloride                         and acrylamide                                                                Copolymer (27:63) of dimethyldiallylammonium chloride                         and acrylamide                                                                Copolymer (13:87) of dimethyldiallylammonium chloride                         and acrylamide                                                                Copolymer (7:93) of dimethyldiallylammonium chloride                          and acrylamide                                                                Copolymer (90:10) of dimethyldiallylammonium chloride                         and diacetone acrylamide                                                      Copolymer (95:5) of dimethyldiallylammonium chloride                          and diacetone acrylamide                                                      ______________________________________                                    

The compositions were evaluated by applying them to tresses of bothvirgin and bleached/waved hair and allowing them to stand for 20minutes. After rinsing and shampooing, the tresses displayed the samesuperior condition as observed in the other examples in contrast to theundesirable condition of tresses treated with similar compositionsomitting the polymer.

Also useful in the present invention in addition to the polymers andcopolymers specifically described above are various other polymers andcopolymers described in U.S. Pat. Nos. 3,288,770 and 3,412,019;particularly effective are a homopolymer ofmethyl-beta-propionamidodiallylammonium chloride as well as a copolymermade from 75:25 by weight mixture of dimethyldiallylammonium chlorideand of methyldodecyldiallylammonium chloride and a copolymer made from50:50 by weight mixture of these monomers. These polymers and copolymerscan be substituted in the foregoing examples with only slightdifferences in degree of effectiveness of the resultant cosmeticcomposition.

What is claimed is:
 1. A hair bleaching composition containing, inaddition to a bleaching agent,water and a water soluble polymer having amolecular weight from 20,000 to 3,000,000 and having a molecular chaincontaining units selected from the group consisting of ##STR5## whereinR is hydrogen or methyl; R' is hydrogen, alkyl having one to twenty-twocarbon atoms, lower hydroxyalkyl having from one to five carbon atoms,or lower alkyl containing a terminal amido group; and A and B areindependently alkyl having from one to twenty-two carbon atoms, lowerhydroxyalkyl or lower alkyl containing a terminal amido group, orwherein A and B taken together with N are piperidinyl or morpholinyl,the amount of said polymer being from 0.05% to 40% by weight of thetotal composition.
 2. The composition as claimed in claim 1 in which Aand B are both methyl.
 3. The composition as claimed in claim 1 in whichA and B are both ethyl.
 4. The composition as claimed in claim 1 inwhich the polymer contains in addition up to 95% by weight of the totalof units selected from the group consisting of ##STR6##
 5. Thecomposition as claimed in claim 4 in which A and B are both methyl. 6.The composition as claimed in claim 1 in which the polymer ispolydiallyldiethylammonium chloride.
 7. The composition for bleachinghair as claimed in claim 1 containing as the bleaching agent a memberselected from the group consisting of hydrogen peroxide and ureahydrogen peroxide in an amount from 0.5 to 20% by weight of the totalcomposition.
 8. The composition as claimed in claim 7 containing inadditiona surface active agent in an amount from 0.1 to 50% by weight ofthe total composition and a water miscible hydroxylated aliphaticsolvent sufficient to solubilize all of the ingredients, the amount ofsaid solvent being from 1 to 90% by weight of the total composition. 9.The composition as claimed in claim 8 in which A and B are both methyl.10. The composition as claimed in claim 8 in which A and B are bothethyl.
 11. The composition as claimed in claim 8 in which the polymercontains in addition up to 95% by weight of the total of units selectedfrom the group consisting of ##STR7##
 12. The composition as claimed inclaim 11 in which A and B are both methyl.
 13. The composition asclaimed in claim 8 in which the polymer is polydiallyldiethylammoniumchloride.
 14. A process of bleaching hair which comprises applyingthereto an effective amount of the composition as claimed in claim 1.